CN105887127A - Method for preparing chloromethyl pyridine derivative by electrochemical selective dechloridation - Google Patents
Method for preparing chloromethyl pyridine derivative by electrochemical selective dechloridation Download PDFInfo
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Abstract
The invention discloses a method for preparing a chloromethyl pyridine derivative by electrochemical selective dechloridation. The method comprises the following steps: taking an acidic solution as a reaction medium, and adding a trichloromethyl pyridine derivative as shown in formula (I) into the acidic solution to obtain an electrolytic reaction solution; carrying out electrolytic reaction in an electrolytic cell which takes a carbon material as a cathode and takes a chemical inert conductive material or a titanium metal material coated with a noble metal oxide as an anode at a temperature being 20-40 DEG C, wherein the current density is 0.5-10A/dm<2>, and the pH is equal to 1-6; and after the electrolytic reaction is ended, separating and purifying to obtain the chloromethyl pyridine derivative as shown in formula (II). The method realizes carrying out hydrogenation reduction on the trichloromethyl pyridine derivative with relatively high chemical selection (greater than or equal to 75%) and a relatively high yield (greater than or equal to 70%) to obtain the chloromethyl pyridine derivative, so that mercury and zinc powder with high toxicity are avoided, constant-current electrolysis is realized, and electrolytic potential is not needed to be controlled, and therefore, the method is beneficial for industrial production.
Description
(1) technical field
The present invention relates to the electrochemistry selectivity dechlorination method of a kind of trichloromethyl pyridine derivant, specifically
Relate to chlorine substituent on electrochemistry selective hydration trichloromethyl pyridine derivant methyl and prepare chloromethyl
The method of pyridine derivate.
(2) background technology
Chloromethyl pyridine derivative as shown in formula (II) is very important pesticide or medicine intermediate,
Such as 2-vhloro-5-chloromethylpyridine be produce imidacloprid, fluazifop etc. efficiently, low toxicity, low residual
Stay the key intermediate of novel pesticide.
In formula (I), X is H, F, CN, NR2Or OR, wherein R is H, C1～C6
Alkyl, phenyl ring, fluorobenzene ring or chlorobenzene ring, n is 0 or 1；M is 0,1,2,3 or 4；
The same formula of X, m and n (I) in formula (II).
It is short that chloridising preparation chloromethyl pyridine derivative as shown in formula (II) has technological process, useless
The advantage that water is few, is one of most potential industrialized preparing process.The greatest problem of restriction the method
It is: depth of chlorination is not easily controlled.This causes the trichloromethyl pyridine derivant as shown in formula (I)
A large amount of generations.
Cannot break through if depth of chlorination controls technology, will be as shown in formula (I) with hydro-reduction method
Trichloromethyl pyridine derivant to change into the chloromethyl pyridine derivative as shown in formula (II) will be one
The preferable alternative route of bar.In order to realize this route, Japan Patent (grant number: 3123815)
Zinc powder reduction method is have developed by formula (I) institute with United States Patent (USP) (grant number: 5475112) etc.
The trichloromethyl pyridine derivant dechlorination shown becomes the chloromethyl pyridine derivative shown in formula (II).The party
The major defect of method is: reaction can produce a large amount of irretrievable high COD brine waste.
Use in sulphuric acid/methanol aqueous solution it addition, United States Patent (USP) (grant number 3687827) reports
Electrochemical reduction method reductase 12,3,4,5-tetra-chloro-6-trichloromethyl pyridine prepares the chloro-6-of 2,3,4,5-tetra-bis-
The method of chloromethylpyridine.The method has and does not produces brine waste and the high advantage of yield.Its maximum
Shortcoming is the shortcoming (generation that cathode material have employed highly toxic mercury metal and product extraction comparison difficulty
Chloro-pyridine sulfate need neutralize after could extract).Acta PhySico-Chimica Sinica [Acta Phys.-Chim.
Sin.2013,29 (5), 973-980] report the electrochemical reduction mistake of benzenyl trichloride in acetonitrile solution
Journey, finds have a large amount of dimer to generate in addition to generating xylylene dichlorides and chloromethyl benzene.
(3) summary of the invention
It is an object of the present invention to provide a kind of electrochemistry selectivity dechlorination and prepare chloromethyl pyridine derivative
Method, with the material with carbon element such as graphite, activated carbon as negative electrode, molten by water, C1～C4 alcohol, acetonitrile etc.
To various such as formula (I) in the acid solution of agent and the supporting electrolyte such as benzene sulfonic acid sodium salt, lithium chloride composition
Shown trichloromethyl pyridine derivant carries out electrolytic experiment, by controlling above-mentioned cell reaction liquid
PH=1～6, various trichloromethyl pyridine derivants can optionally be reduced into such as formula (II) institute
The chloromethyl pyridine derivative shown, the trichloromethyl pyridine that the present invention solves as shown in formula (I) spreads out
" the low height that are difficult to reclaim a large amount of with generation of zinc powder utilization rate of the biological existing recovery and utilization technology of by-product
COD Containing Zinc Chloride waste water " problem and existing Electrochemical hydriding dechlorination technology process trichloromethyl pyridine
Analog derivative " uses highly toxic mercury metal ", " product extraction comparison difficulty " and " hydrodechlorination choosing
Selecting property is low " problem.
The technical solution used in the present invention is:
The present invention provides a kind of method that chloromethyl pyridine derivative is prepared in electrochemistry selectivity dechlorination, institute
The electrochemistry selectivity dechlorination method stated is: with acid solution as reaction medium, by formula (I) Suo Shi
Trichloromethyl pyridine derivant add in acid solution and obtain cell reaction liquid, with carbon materials be
Negative electrode, electricity with the titanium metal material of chemical inertness conductive material or noble metal-coating oxide as anode
Solving in groove and carry out cell reaction, temperature is 20～40 DEG C, and electric current density is 0.5～10A/dm2,
PH=1～6, after cell reaction terminates, obtains the chloromethylpyridine shown in formula (II) through isolated and purified
Derivant；Described acid solution is formed by solvent and supporting electrolyte mixed preparing, Qi Zhongsuo
The solvent stated is that the mixing of water and the mixed solvent of proton polar solvent, water and aprotic polar solvent is molten
Agent or water, proton polar solvent and the mixed solvent of aprotic polar solvent composition；Described support electricity
The salt of one or both arbitrary proportions mixing that Xie Zhiwei is dissolvable in water in solvent；
In formula (I), X is H, F, CN, NR2Or OR, wherein R is H, C1～C6
Alkyl, phenyl ring, fluorobenzene ring or chlorobenzene ring, n is 0 or 1；M is 0,1,2,3 or 4；
The same formula of X, m and n (I) in formula (II).
Cell reaction liquid of the present invention is in course of reaction, and pH controls, 1～6, preferably to control
2～5.
Cathode material of the present invention be diamond, graphite or amorphous carbon, preferably graphite be negative electrode
Material.Described cathode shape is tabular, fiber cloth-like, felted or graininess, preferably tabular.More excellent
Selecting described carbon materials is graphite cake, tabletting activated carbon, carbon felt, graphitization carbon felt or carbon cloth.
Trichloromethyl pyridine derivant shown in formula of the present invention (I) includes: 2-chloro-5-trichloromethyl
Pyridine, 2,3-bis-chloro-5-trichloromethylpyridine, 2,6-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetrachloro
-5-trichloromethyl pyridine, 2-chloro-6-amino-5-trichloromethyl pyridine, 2-chloro-6-dimethylamino-5-trichlorine
The chloro-3-of picoline, 2-fluoro-5-trichloromethyl pyridine, the chloro-6-of 2-fluoro-5-trichloromethyl pyridine, the chloro-3-of 2-
Methoxyl group-5-trichloromethyl pyridine, 2-fluoro-5-trichloromethyl pyridine, 2-cyano group-5-trichloromethyl pyridine,
2-hydroxyl-5-trichloromethyl pyridine, 2-phenoxy group-5-trichloromethyl pyridine, 2-(4-fluorophenoxy)-5-three
Chloromethylpyridine, 2-(3-fluorophenoxy)-5-trichloromethyl pyridine and 2-(3-chlorophenoxy)-5-three chloromethane
Yl pyridines.
Further, described including dispensing polar solvent is C1～C4 Organic Alcohol, described C1～C4
Organic Alcohol is preferably methanol, ethanol, normal propyl alcohol or isopropanol, more preferably methanol；Described including dispensing
Solvent mass content in described cell reaction liquid is 0～90%, preferably 50～80%；Described is non-
Proton polar solvent is acetonitrile, dimethylformamide (DMF) or dimethyl sulfoxide (DMSO)；
Described non-protonic solvent mass content in described cell reaction liquid is 0～80%, preferably
30～50%.
Further, described supporting electrolyte is cation and the salt of anion composition, described cation
Including: sodium ion, potassium ion, lithium ion, ammonium radical ion and organic ammonium radical ion；Described anion
Including: chloride ion, fluorion, sulfate ion, perchlorate and organic sulfonic acid radical ion,
Preferred as alkali ion is as cation, and preferably halide ion is as cation, more preferably supports electrolysis
Matter is one of following or two kinds and the mixing of any of the above ratio: lithium chloride, potassium fluoride, sodium fluoride,
Ammonium chloride or tetrabutylammonium perchlorate；Described supporting electrolyte content in described cell reaction liquid is
0.05～2mol/L, preferably 0.1～1mol/L.
Further, the most described acid solution is one of aqueous solution of following mixture, each in mixture
The consumption of individual composition is in terms of cell reaction liquid gross mass: (1) 0.5mol/L lithium chloride+80% methanol；
(2) 0.5mol/L lithium chloride+50% methanol+30% acetonitrile；(3) 0.5mol/L lithium chloride+80% first
Alcohol；(4) 0.5mol/L lithium chloride+90% ethanol；(5) 0.2mol/L lithium chloride+0.2mol/L benzene
Sodium sulfonate+50% isopropanol+30% dimethyl sulfoxide；(6) 0.1mol/L tetraethyl ammonia perchlorate
+ 10% butanol+85% dimethylformamide；(7) 0.05mol/L ammonia perchlorate+10% ethanol
+ 80% acetonitrile；(8) 0.1mol/L potassium hyperchlorate+80% acetonitrile；(9)0.2mol/L LiCl+0.1
Mol/L sodium tetrafluoroborate+10% acetonitrile+80% methanol；(10) 0.05mol/L LiCl+50%
Isopropanol+30% acetonitrile；(11) 0.5mol/L LiCl+40% isopropanol+50% acetonitrile；(12)2
Mol/L LiCl+50% isopropanol+30% acetonitrile.
Anode material of the present invention is not the key factor of the present invention, can be that any chemical inertness is led
Electric material, such as platinum, graphite, carbon or conductive plastics.Anode also can be by being coated on another kind of material
Coating forms, such as: be applied on titanium by the metal oxide containing precious metals of such as ruthenium-oxide etc.
The shape of described anode can be tabular, shaft-like, wire shape, mesh-like, netted, cystose,
Ulotrichy or the form of lamellar, the mesh-like of preferred development.
Cell reaction of the present invention can intermittently carry out or carry out in continuously or semi-continuously mode.Electrolysis
Groove can be the agitator tank containing electrode or the flow cell channel of any traditional design.Electrolysis bath can be
Single chamber groove can also diaphragm cell, preferably diaphragm cell.Available separator material has, various
Anion or cation exchange membrane, the Teflon of porous, asbestos or glass, preferably perfluorinated sulfonic acid sun from
Sub-film is as the barrier film of electrolysis bath.
Although preferably releasing oxygen as anode reaction, but other anodes many can also be used anti-
Should.Including chlorine molecule and the protectiveness releasing or passing through such as formates or oxalates etc of molecular bromine
The oxidation of material produces carbon dioxide or is formed valuable by the oxidation of organic reactant
By-product.
During cell reaction of the present invention, with cell reaction liquid as catholyte, with 1mol/L sulphuric acid water
Solution or 1mol/L lithium hydroxide aqueous solution are anolyte.
During described cell reaction, corresponding electric current density is according to trichloromethyl in cell reaction liquid
The concentration change of pyridine derivate and change, the electrolysis cathode electric current density generally being suitable for is 0.5～10
A/dm2, preferably 1～4A/dm2.Described trichloromethyl pyridine derivant is in described cell reaction liquid
Content be 0.05～1mol/L, preferably 0.1～0.5mol/L.
Temperature is not the key factor of the present invention, and cell reaction can be carried out at-10～90 DEG C, it is considered to molten
Dissolubility in cell reaction liquid of the volatilization of agent, reactant and the electric conductivity of cell reaction liquid, preferably
20～40 DEG C of temperature as cell reaction.
The present invention carries out required electroreduction by one conventionally known in the art.Usually, will
Raw material chloromethylpyridine derivative dissolves or is partially dissolved in solvent, adds a certain amount of support electricity
Xie Zhi, is then passed through enough electric currents in electrolyzer, until obtaining the reduction of desirable degree, and electrolysis
After reaction terminates, traditional technology is utilized to reclaim product.Such as, first steam easily by the method for distillation
The organic solvent (such as methanol) of volatilization, then extracts steaming remaining liquid with toluene, finally uses rectification
Method obtain required product.
Compared to existing technology, the beneficial effects are mainly as follows: (1) uses first with inexpensively
The carbon materials of environmental protection is the electrochemical method of negative electrode, it is achieved that trichloromethyl pyridine derivant highizationer
Learn selectivity (>=75%) with higher yields (>=70%) hydro-reduction become chloromethyl pyridine to spread out
Biological.(2) electrode material that the method uses avoids highly toxic hydrargyrum.(3) course of reaction does not makes
With zinc powder, thus avoid the generation of a large amount of intractable high COD Waste Containing Zinc Chloride.(4) real
Having showed constant-current electrolysis, electrolytic potential need not control, thus beneficially industrialized production.(5) produce
Thing extracts and avoids neutralization procedure.
(4) detailed description of the invention
Below in conjunction with specific embodiment and comparative example [all embodiments and the high performance liquid chromatography of comparative example
Analysis condition is all: C18 symmetrical posts (250mm length_4.6mm i.d., 5mm particle size)
For detached dowel；Acetonitrile/methanol/water (volume ratio 1:3:6) mixed solution is flowing phase；Flow velocity is:
1mL/Min；Detection wavelength is 230nm；Waters 2996PDA is detector.] to the present invention
It is described further, but protection scope of the present invention is not limited to that:
Embodiment 1 is electrolysed 2-chloro-5-trichloromethylpyridine (CTC) synthesis 2-vhloro-5-chloromethylpyridine
(CCMP)
Barrier film sheet frame groove is electrolysis reactor, and perfluoro sulfonic acid membrane is barrier film, and graphite cake is negative electrode, graphite
Plate is anode.1000mL 0.2mol/L CTC+0.5mol/L LiCl+80wt% methanol water-soluble
Liquid is catholyte；1mol/L aqueous sulfuric acid is anolyte.In electrolytic process, temperature control is
20～25 DEG C, electric current density controls as 2A/dm2, catholyte pH=2～4.It is passed through 12F/mol CTC
Electrolysis is stopped after electricity.Obtain with high-efficient liquid phase analysis after catholyte being diluted 1000 times with methanol:
CCMP yield is 65%, and selectivity is 70%.
Embodiment 2 is electrolysed 2-chloro-5-trichloromethylpyridine (CTC) synthesis 2-vhloro-5-chloromethylpyridine
(CCMP)
Barrier film sheet frame groove is electrolysis reactor, and perfluoro sulfonic acid membrane is barrier film, and graphite cake is negative electrode, and titanium plates
Ruthenium net is anode.1000mL 0.2mol/L CTC+0.5mol/L LiCl+50wt% methanol+30
The aqueous solution of wt% acetonitrile is catholyte；1mol/L lithium hydroxide aqueous solution is anolyte.It was electrolysed
Cheng Zhong, it is 35～40 DEG C that temperature controls, and electric current density controls as 2A/dm2, catholyte pH=2～4.
Electrolysis is stopped after being passed through 12F/mol CTC electricity.With height after catholyte being diluted 1000 times with methanol
Effect liquid phase analysis obtains: CCMP yield is 63%, and selectivity is 69%.
Comparative example 1 (comparative example 1) electrolysis 2-chloro-5-trichloromethylpyridine (CTC) synthesis 2-
Chlorine-5-chloromethyl pyridine (CCMP)
Barrier film sheet frame groove is electrolysis reactor, and perfluoro sulfonic acid membrane is barrier film, and plating hydrargyrum copper coin is negative electrode, stone
Ink plate is anode.The water of 1000mL 0.2mol/L CTC+0.5mol/L LiCl+80wt% methanol
Solution is catholyte；1mol/L aqueous sulfuric acid is anolyte.In electrolytic process, temperature control is
20～25 DEG C, electric current density controls as 2A/dm2, catholyte pH=2～4.It is passed through 12F/mol CTC
Electrolysis is stopped after electricity.Obtain with high-efficient liquid phase analysis after catholyte being diluted 1000 times with methanol:
CCMP yield is 3%, and selectivity is 3%.
Comparative example 2 (comparative example 2) electrolysis 2-chloro-5-trichloromethylpyridine (CTC) synthesis 2-
Chlorine-5-chloromethyl pyridine (CCMP)
Barrier film sheet frame groove is electrolysis reactor, and perfluoro sulfonic acid membrane is barrier film, and graphite cake is negative electrode, graphite
Plate is anode.1000mL 0.2mol/L CTC+0.5mol/L LiCl+50wt% methanol+30
The aqueous solution of wt% acetonitrile is catholyte；1mol/L lithium hydroxide aqueous solution is anolyte.It was electrolysed
Cheng Zhong, it is 35～40 DEG C that temperature controls, and electric current density controls as 2A/dm2, catholyte pH=0～1.
Electrolysis is stopped after being passed through 12F/mol CTC electricity.With height after catholyte being diluted 1000 times with methanol
Effect liquid phase analysis obtains: CCMP yield is 5%, and selectivity is 99%.
Embodiment 3～embodiment 11
Embodiment 3～embodiment 11 are carried out according to the experiment parameter of table 1, and remaining operation is with embodiment 1.
Table 1 1000mL scale electrolysis 2-chloro-5-trichloromethylpyridine (CTC) synthesis 2-chloro-5-chlorine
The experiment condition of picoline (CCMP) and result
Embodiment 12～embodiment 21
Embodiment 12～embodiment 21 are carried out according to the experiment parameter of table 2, and remaining operates same embodiment
1。
Table 2 1000mL scale is electrolysed various trichloromethyl pyridine derivants and synthesizes a corresponding chloromethane
The experiment condition of pyridine derivative and result
Claims (10)
1. the method that chloromethyl pyridine derivative is prepared in an electrochemistry selectivity dechlorination, it is characterised in that institute
The electrochemistry selectivity dechlorination method stated is: with acid solution as reaction medium, by three shown in formula (I)
Chloromethyl pyridine derivative adds in acid solution and obtains cell reaction liquid, with carbon materials as negative electrode,
Electrolysis bath with the titanium metal material of chemical inertness conductive material or noble metal-coating oxide as anode enters
Row cell reaction, temperature is 20～40 DEG C, and electric current density is 0.5～10A/dm2, pH=1～6, electrolysis is anti-
After should terminating, obtain the chloromethyl pyridine derivative shown in formula (II) through isolated and purified；Described acid
Property solution is formed by solvent and supporting electrolyte mixed preparing, and wherein said solvent is water and proton
The mixed solvent of the mixed solvent of polar solvent, water and aprotic polar solvent or water, proton polar solvent
Mixed solvent with aprotic polar solvent composition；Described supporting electrolyte is to be dissolvable in water in solvent
The salt of one or both arbitrary proportions mixing；
In formula (I), X is H, F, CN, NR2Or OR, wherein R is the alkane of H, C1～C6
Base, phenyl ring, fluorobenzene ring or chlorobenzene ring, n is 0 or 1；M is 0,1,2,3 or 4；Formula (II)
Middle X, n and m same formula (I).
2. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1, its
It is characterised by that described carbon materials is diamond, graphite or amorphous carbon.
3. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1, its
It is characterised by that described cathode shape is tabular, fiber cloth-like, felted or graininess.
4. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 3, its
It is characterised by that described carbon materials is graphite cake, tabletting activated carbon, carbon felt, graphitization carbon felt or carbon fiber
Cloth.
5. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1, its
It is characterised by that described cell reaction liquid pH in course of reaction controls 2～5.
6. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1, its
The proton polar solvent being characterised by described is C1～C4 Organic Alcohol；Described proton polar solvent is at described electricity
The mass content solved in reactant liquor is 0～90%；Described aprotic polar solvent is acetonitrile, dimethyl methyl
Amide or dimethyl sulfoxide；Described non-protonic solvent mass content in described cell reaction liquid is
0～80%.
7. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1, its
The supporting electrolyte being characterised by described is cation and the salt of anion composition, and described cation includes:
Sodium ion, potassium ion, lithium ion, ammonium radical ion and organic ammonium radical ion；Described anion includes: chlorine
Ion, fluorion, perchlorate and organic sulfonic acid radical ion；Described supporting electrolyte is at described electricity
The content solved in reactant liquor is 0.1～2mol/L.
8. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1, its
It is characterised by that described supporting electrolyte is lithium chloride, potassium fluoride, sodium fluoride, ammonium chloride or tetrabutyl height chlorine
One or both and the mixing of any of the above ratio in acid ammonium.
9. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1, its
It is characterised by that shown in described formula (I), trichloromethyl pyridine derivant content in cell reaction liquid is
0.05～1mol/L.
10. the method that pyridine derivatives is prepared in electrochemistry selectivity dechlorination as claimed in claim 1,
It is characterized in that one of aqueous solution that described acid solution is following mixture, each composition in mixture
Consumption is in terms of cell reaction liquid gross mass: (1) 0.5mol/L lithium chloride+80% methanol；(2)0.5mol/L
Lithium chloride+50% methanol+30% acetonitrile；(3) 0.5mol/L lithium chloride+90% ethanol；(4)0.2mol/L
Lithium chloride+0.2mol/L benzene sulfonic acid sodium salt+50% isopropanol+30% dimethyl sulfoxide；(5)0.1mol/L
Tetraethyl ammonia perchlorate+10% butanol+85% dimethylformamide；(6) 0.05mol/L ammonia perchlorate
+ 10% ethanol+80% acetonitrile；(7) 0.1mol/L potassium hyperchlorate+80% acetonitrile；(8)0.2mol/L
LiCl+0.1mol/L sodium tetrafluoroborate+10% acetonitrile+80% methanol；(9)0.05mol/L
LiCl+50% isopropanol+30% acetonitrile；(10) 0.5mol/L LiCl+40% isopropanol+50% acetonitrile；
(11) 2mol/L LiCl+50% isopropanol+30% acetonitrile.
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| CN110172710A (en) * | 2019-04-15 | 2019-08-27 | 浙江工业大学 | A kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters |
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| CN110172710A (en) * | 2019-04-15 | 2019-08-27 | 浙江工业大学 | A kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters |
| CN110172710B (en) * | 2019-04-15 | 2020-08-14 | 浙江工业大学 | Method for preparing carboxylic ester by electrochemical dechlorination of trichloromethylpyridine derivative |
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